Nu-acyl derivatives of cyclic imines



United States Patent 8 Claims. (Cl. 260294.7)

This application is a division of Serial No. 361,925, filed April 2,1964, now US. Patent No. 3,248,296, which was a division of Serial No.260,923, filed February 25, 1963, now United States Patent No.3,219,612.

A non-exclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the UnitedStates Government, with the power to grant sublicenses for such,purposes, is hereby granted to the Government of the United States ofAmerica.

This invention relates to certain compounds which are N-acyl derivativesof cyclic imines, to some unique mixtures of N-acyl derivatives ofcyclic imines, and to plastic compositions, the plasticizer component ofwhich is at least one of the compounds or one of the unique mixturesthat are the subject of this invention. More particularly, thisinvention relates to N,N-disubstituted long chain aliphatic amides theacyl component of which if saturated is an alkanoic acyl containing from10 to 18 carbon atoms, and if unsaturated is an alkenoic acyl containingfrom 18 to 22 carbon atoms, the amide nitrogen in all cases being amember of a heterocyclic ring or in the case of a fused ring system oneof the heterocyclic rings, all of the other ring members being carbon ornitrogen atoms.

The invention to which the present application is specifically directedrelates to certain long-chain fatty acid amides of unsubstituted andalkyl-substituted piperidines.

We have discovered that the compounds that are the subject of thisinvention are good, compatible, solventtype plasticizers for vinylchloride resins. these compounds are effici'ent primary solvent-typeplasticizers which can be made from low price fatty acids and whichexhibit good compatibility with and impart low volatility loss,resistance to microbial action, excellent low temperature properties,and stability to northern light exposure to polymer and copolymer resinsof vinyl chloride.

The terms vinyl type resin and vinyl chloride resin are used throughoutthis specification to refer to polymers and copolymers of monomerscontaining vinyl chloride in a predominant proportion by weight. Termssuch as compatible, good compatibility, and compatible plasticizer inreference to the plasticizers which are the subject of this inventionare used throughout the specification to refer to plasticizers that showno sign of exudation, migration to the surface, for at least two weekswhen the plasticizers are present in the resin in proportions of about70 parts by weight of plasticizer to 100 parts by weight of resin.

Not only are the compounds that are the subject of this invention usefulas plasticizers for vinyl chloride resins, but they are also efficient,compatible softeners for Buna N rubber, imparting low volatility lossand excellent low temperature properties to the plasticized rubbercompositions.

If a resin is plasticized with a compound with which it has only limitedcompatibility, the plasticizer soon exudes or migrates to the surfaceunless the plasticizer is used either in a limited amount or is used inconjunction Moreover,

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with a mutual solvent (a compatible auxiliary plasticizer) to obtainadequate compatibility. g

It is known in the art that compounds similar to those which are thesubject of this invention exhibit reasonably good compatibilty forhydrophylic type resins but in order to obtain adequate flexibility mustbe employed together with a secondary or an auxiliary plasticizer asseen for example in United States Patent Number 2,339,056.

It would be expected from the recognized compatibility of compoundsrelated to the type herein described with polyvinyl acetals (hydrophylictype resins), that these compounds would be quite incompatible withpolymers of the vinyl chloride type. We have discovered, however, thatnot only are the particular compounds and compound mixtures hereindescribed compatible as primary plasticizers with vinyl chloride resinsbut as we note above they are compatible with the hydrophylic typeresins as well.

The specific component ratio of compatible compositions can beestablished according to the scheme set forth in our US. Patent No.3,219,664, for example.

The compounds that are the subject of this invention are convenientlyprepared by reacting the appropriate piperidine compound with theappropriate acid or corresponding acid chloride. In any event, methodsfor preparing compounds such as those herein described are well known tothose skilled in the art of fatty acid chemistry.

.The details of individual preparations are listed in the operatingexamples which follow:

EXAMPLE 1 N-oleoylpiperidine.Twenty-two and four-tenths grams (0.26mole) of piperidine were dissolved in 60 milliliters of benzene and 39.7grams (0.13 mole) of oleoyl chloride were added dropwise with stirring.After stirring for an additional hour, the reaction mixture wasfiltered, washed successively with dilute hydrochloric acid and water,and dried over anhydrous sodium sulfate. Free acid was removed bypercolating the benzene solution through a column of activated aluminaand eluting the amide with a 1:1 ethanol-benzene mixture. The solventwas then removed by stripping under reduced pressure. Analysis of theproduct, N-oleoylpiperidine: Percent C, 78.15 (theory 78.95); percent H,12.07 (theory 12.40); percent N, 4.04 (theory 4.04).

EXAMPLE 2 N-oleoyl-Z-methylpiperidine.-A mixture of 31.6 grams (0.32mole) of Z-methylpiperidine, 60 grams (0.21 mole) of oleic acid, and 20milliliters of benzene was refluxed in an apparatus equipped with aDean-Stark trap until the evolution of water ceased. The reactionmixture was diluted with milliliters of commercial hexane, Washedsuccessively with dilute hydrochloric acid and water, and dried overanhydrous sodium sulfate. Free acid was removed by percolating thehexane solution through .a column of activated alumina, and eluting theamide with a 1:1 hexane-ethanol mixture. The solvent was removed bystripping under reduced pressure. Analysis of the product,N-oleoyl-2-methylpiperidine: Percent C, 78.87 (theory 79.20); percent H,12.13 (theory 12.47); percent N, 3.86 (theory 3.85).

EXAMPLE 3 N oleoyl 3 methylpiperidine.N-oleoyl 3 methylpiperidine wasprepared by the procedure of Example 2 from 31.6 grams (0.32 mole) of3-methylpiperidine, and 60 grams (0.21 mole) of oleic acid. Analysis ofthe product, N-oleoy1-3-methylpipe'ridine: Percent C, 79.03 (theory79.20); percent H, 12.30 (theory 12.47); percent N, 3.89 (theory 3.85).

EXAMPLE 4 N oleoyl 4 methylpipe'ridiner -N oleoyl 4 methylpiperidine wasprepared by the procedure of Example 2 from 31.6 grams (0.32 mole) of4-methylpiperidine and '60 grams (0.21 mole) of oleic acid. Analysis ofthe product, N-oleoyl-4-methylpiperidine: Percent C, 78.80 (theory79.20); percent H, 12.08 (theory 12.47); percent N, 3.86 (theory 3.85).

EXAMPLE 5 N oleoyl 4 ethylpiperidine.N oleoyl 4 ethylpiperidine wasprepared by the procedure of Example 2 from 14.4 grams (0.13 mole) of4-ethylpiperidine and 30 grams (0.11 mole) of oleic acid. Analysis ofthe prod-net, N-oleoyl-4-ethylpiperidine: Percent C, 79.17 (theory79.45); percent H, 12.62 (theory 12.45); percent N, 3.75 (theory 3.71).

EXAMPLE 6 N oleoyl 2 methyl 5 ethylpiperidine.-N oleoyl-2-methy1-5-ethylpiperidine 'was prepared from 27 grams (0.21 mole) of2-methyl-S-ethylpiperidine and 40 grams (0.14 mole) of oleic acid byExample 2, except that toluene was used as the entrajning solvent.Analysis of the product, N-01eoyl-2-methyl-5-ethylpiperidine: Percent C,79.51 (theory 79.66); percent H, 12.40 (theory 12.51); percent N, 3.79(theory 3.85).

EXAMPLE 7 N oleoyl 2,6 dimethylpiperidine.N oleoyl 2,6-dirnethylpiperidine was prepared by the procedure of Example 1 from 30.1grams (0.27 mole) of 2,6-dimethylpiperidine, and 40 grams (0.13 mole) ofoleoyl chloride. Analysis of the product,N-oleoy1-2,6-dimethylpiperidine:

4 Percent C, 79.19 (theory 79.12); percent H, 12.43 (theory 12.30);percent N, 3.74 (theory 3.72).

EXAMPLE 8 5 N decanoyl 4 n0nylpiperidine.N decanoyl 4- nonylpiperidinewas prepared by the procedure of Exampie 2 from 53 grams (0.25 mole) of4-nonylpiperidine and 40 grams (0.23 mole) of decanoic acid. Analysis ofthe product, N-decanoyl-4-nonylpiperidine: Percent C, 78.69 (theory78.78); percent H, 12.90 (theory 12.96); percent N, 3.76 (theory 3.83).

We claim:

. N-oleoylpiperidine. N-oleoyl-2-methylpiperidine.N-oleoyl-3-methylpiperidine. N-oleoyl-4-methylpiperidine.N-o1eoyl-4-ethylpiperidine. N-oleoyl-2-methy1-5-ethylpiperidine.

N-oleoyl-2,6-dimethylpiperidine. N-decanoyl-4-nonylpiperidine.

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1. N-OLEOYLPIPERIDINE.